Frequency Electron Paramagnetic Resonance Research Articles

Heterometallic CoIII4FeIII2Schiff Base Complex: Structure, Electron Paramagnetic Resonance, and Alkane Oxidation Catalytic Activity

The heterometallic complex [Co(4)Fe(2)OSae(8)]·4DMF·H(2)O (1) was synthesized by one-pot reaction of cobalt powder with iron chloride in a dimethylformamide solution of salicylidene-2-ethanolamine (H(2)Sae) and characterized by single crystal X-ray diffraction analysis, magnetic measurements, high frequency electron paramagnetic resonance (HF-EPR), and Mössbauer spectroscopies. The exchange coupling in the Fe(III)-Fe(III) pair is of antiferromagnetic behavior with J/hc = -190 cm(-1). The HF-EPR spectra reveal an unusual pattern with a hardly detectable triplet signal of the Fe(III) dimer. The magnitude of D (ca. 13.9 cm(-1)) was found to be much larger than in related dimers. The catalytic investigations disclosed an outstanding activity of 1 toward oxidation of cycloalkanes with hydrogen peroxide, under mild conditions. The most efficient system showed a turnover number (TON) of 3.57 × 10(3) with the concomitant overall yield of 26% for cyclohexane, and 2.28 × 10(3)/46%, respectively, for cyclooctane. A remarkable turnover frequency (TOF) of 1.12 × 10(4) h(-1) (the highest initial rate W(0) = 3.5 × 10(-4) M s(-1)) was achieved in oxidation of cyclohexane. Kinetic experiments and selectivity parameters led to the conclusion that hydroxyl radicals are active (attacking C-H bonds) species. Kinetic and electrospray ionization mass spectrometry (ESI-MS) data allowed us to assume that the trinuclear heterometallic particle [Co(2)Fe(Sae)(4)](+), originated from 1 in solution, could be responsible for efficient generation of hydroxyl radicals from hydrogen peroxide.

Electron tunneling in lithium-ammonia solutions probed by frequency-dependent electron spin relaxation studies.

Electron transfer or quantum tunneling dynamics for excess or solvated electrons in dilute lithium-ammonia solutions have been studied by pulse electron paramagnetic resonance (EPR) spectroscopy at both X- (9.7 GHz) and W-band (94 GHz) frequencies. The electron spin-lattice (T(1)) and spin-spin (T(2)) relaxation data indicate an extremely fast transfer or quantum tunneling rate of the solvated electron in these solutions which serves to modulate the hyperfine (Fermi-contact) interaction with nitrogen nuclei in the solvation shells of ammonia molecules surrounding the localized, solvated electron. The donor and acceptor states of the solvated electron in these solutions are the initial and final electron solvation sites found before, and after, the transfer or tunneling process. To interpret and model our electron spin relaxation data from the two observation EPR frequencies requires a consideration of a multiexponential correlation function. The electron transfer or tunneling process that we monitor through the correlation time of the nitrogen Fermi-contact interaction has a time scale of (1-10) × 10(-12) s over a temperature range 230-290 K in our most dilute solution of lithium in ammonia. Two types of electron-solvent interaction mechanisms are proposed to account for our experimental findings. The dominant electron spin relaxation mechanism results from an electron tunneling process characterized by a variable donor-acceptor distance or range (consistent with such a rapidly fluctuating liquid structure) in which the solvent shell that ultimately accepts the transferring electron is formed from random, thermal fluctuations of the liquid structure in, and around, a natural hole or Bjerrum-like defect vacancy in the liquid. Following transfer and capture of the tunneling electron, further solvent-cage relaxation with a time scale of ∼10(-13) s results in a minor contribution to the electron spin relaxation times. This investigation illustrates the great potential of multifrequency EPR measurements to interrogate the microscopic nature and dynamics of ultrafast electron transfer or quantum-tunneling processes in liquids. Our results also impact on the universal issue of the role of a host solvent (or host matrix, e.g. a semiconductor) in mediating long-range electron transfer processes and we discuss the implications of our results with a range of other materials and systems exhibiting the phenomenon of electron transfer.

Nanoscale magnetic field mapping with a single spin scanning probe magnetometer

We demonstrate quantitative magnetic field mapping with nanoscale resolution, by applying a lock-in technique on the electron spin resonance frequency of a single nitrogen-vacancy defect placed at the apex of an atomic force microscope tip. In addition, we report an all-optical magnetic imaging technique which is sensitive to large off-axis magnetic fields, thus extending the operation range of diamond-based magnetometry. Both techniques are illustrated by using a magnetic hard disk as a test sample. Owing to the non-perturbing and quantitative nature of the magnetic probe, this work should open up numerous perspectives in nanomagnetism and spintronics.

Single-ion anisotropy in Haldane chains and the form factor of theO(3)nonlinear sigma model

We consider spin-1 Haldane chains with single-ion anisotropy, which exists in known Haldane chain materials. We develop a perturbation theory in terms of anisotropy, where magnon-magnon interaction is important even in the low temperature limit. The exact two-particle form factor in the O(3) nonlinear sigma model leads to quantitative predictions on several dynamical properties including dynamical structure factor and electron spin resonance frequency shift. These agree very well with numerical results, and with experimental data on the Haldane chain material Ni(C$_5$H$_{14}$N$_2$)$_2$N$_3$(PF$_6$).

Probing the Local Site Environments in Mn:CdSe Quantum Dots

A quantum dot (QD) contains a well-defined surface passivated by ligands and a bulklike core. The effect of surface passivation and lattice truncation on local structural and electronic microenvironments within a CdSe QD is an area of active research. Selectively probing the local microenvironments that exist at the surface and core of the QD is difficult but can be achieved by use of a Mn(II) impurity ion doped into a CdSe QD using electron paramagnetic resonance (EPR). By use of high frequency EPR (HF-EPR) spectroscopy, the site-dependent perturbation experienced for Mn(II) incorporated as a guest ion into CdSe QDs allows the distinguishing of two unique microenvironments within the QD, namely, an unperturbed core and an electronically distorted surface. Analysis of the Landé g-factor, hyperfine constant (A), and the distribution of g and D (Δg, ΔD) allows the local microenvironments within CdSe to be probed as a function of size, ligand passivation, and site of Mn(II) incorporation.

Autocatalytic O2Cleavage by an OCO3–Trianionic Pincer CrIIIComplex: Isolation and Characterization of the Autocatalytic Intermediate [CrIV]2(μ-O) Dimer

Synthetic and kinetic experiments designed to probe the mechanism of O(2) activation by the trianionic pincer chromium(III) complex [(t)BuOCO]Cr(III)(THF)(3) (1) (where (t)BuOCO = [2,6-((t)BuC(6)H(3)O)(2)C(6)H(3)](3-), THF = tetrahydrofuran) are described. Whereas analogous porphyrin and corrole oxidation catalysts can become inactive toward O(2) activation upon dimerization (forming a μ-oxo species) or product inhibition, complex 1 becomes more active toward O(2) activation when dimerized. The product from O(2) activation, [(t)BuOCO]Cr(V)(O)(THF) (2), catalyzes the oxidation of 1 via formation of the μ-O dimer {[(t)BuOCO]Cr(IV)(THF)}(2)(μ-O) (3). Complex 3 exists in equilibrium with 1 and 2 and thus could not be isolated in pure form. However, single crystals of 3 and 1 co-deposit, and the molecular stucture of 3 was determined using single-crystal X-ray crystallography methods. Variable (9.5, 35, and 240 GHz) frequency electron paramagnetic resonance spectroscopy supports the assignment of complex 3 as a Cr(IV)-O-Cr(IV) dimer, with a high (S = 2) spin ground state, based on detailed computer simulations. Complex 3 is the first conclusively assigned example of a complex containing a Cr(IV) dimer; its spin Hamiltonian parameters are g(iso) = 1.976, D = 2400 G, and E = 750 G. The reaction of 1 with O(2) was monitored by UV-visible spectrophotometry, and the kinetic orders of the reagents were determined. The reaction does not exhibit first-order behavior with respect to the concentrations of complex 1 and O(2). Altering the THF concentration reveals an inverse order behavior in THF. A proposed autocatalytic mechanism, with 3 as the key intermediate, was employed in numerical simulations of concentration versus time decay plots, and the individual rate constants were calculated. The simulations agree well with the experimental observations. The acceleration is not unique to 2; for example, the presence of OPPh(3) accelerates O(2) activation by forming the five-coordinate complex trans-[(t)BuOCO]Cr(III)(OPPh(3))(2) (4).

Pressure and temperature dependence of interlayer spin diffusion and electrical conductivity in the layered organic conductorsκ-(BEDT-TTF)2Cu[N(CN)2]X(X = Cl, Br)

A high frequency (111.2-420 GHz) electron spin resonance study of the inter-layer (perpendicular) spin diffusion as a function of pressure and temperature is presented in the conducting phases of the layered organic compounds, {\kappa}-(BEDT-TTF)2-Cu[N(CN)2]X ({\kappa}-ET2-X), X=Cl or Br. The resolved ESR lines of adjacent layers at high temperatures and high frequencies allows for the determination of the inter-layer cross spin relaxation time, Tx and the intrinsic spin relaxation time, T2 of single layers. In the bad metal phase spin diffusion is two-dimensional, i.e. spins are not hopping to adjacent layers within T2. Tx is proportional to the perpendicular resistivity at least approximately, as predicted in models where spin and charge excitations are tied together. In {\kappa}-ET2-Cl, at zero pressure Tx increases as the bad metal-insulator transition is approached. On the other hand, Tx decreases as the normal metal and superconducting phases are approached with increasing pressure and/or decreasing temperature.

Multiple stable states of a periodically driven electron spin in a quantum dot using circularly polarized light

The periodical modulation of circularly polarized light with a frequency close to the electron spin resonance frequency induces a sharp change of the single electron spin orientation. Hyperfine interaction provides a feedback, thus fixing the precession frequency of the electron spin in the external and the Overhauser field near the modulation frequency. The nuclear polarization is bidirectional and the electron-nuclear spin system (ENSS) possesses a few stable states. The same physics underlie the frequency-locking effect for two-color and mode-locked excitations. However, the pulsed excitation with mode-locked laser brings about the multitudes of stable states in ENSS in a quantum dot. The resulting precession frequencies of the electron spin differ in these states by the multiple of the modulation frequency. Under such conditions ENSS represents a digital frequency converter with more than 100 stable channels.

Spin decoherence in an iron-based magnetic cluster

Continuous wave (cw) and pulsed high frequency electron paramagnetic resonance (HF-EPR) measurements were performed on an Fe-based magnetic cluster: Fe 7O 4(O 2CPh) 11(dmem) 2, abbreviated Fe 7. The cw EPR results show that two different molecular species exist in the crystal, with slightly different zero-field-splitting parameters. The spin decoherence time, T 2, was measured at high magnetic fields and low temperatures, which makes it possible to obtain high spin polarization and to significantly reduce decoherence due to electron spin flip-flop processes. Theoretical fitting of T 2 versus temperature shows that, for crystalline samples of this molecule, spin flip-flop fluctuations represent the main source of spin decoherence at low temperatures, as reported also for the Fe 8 single-molecule magnet [Phys. Rev. Lett. 102 (2009) 087603]. Moreover, it is found that T 2 is position dependent within the EPR line, a model for which is given. We also note that this is the third example of an Fe-based cluster that exhibits a measurable decoherence time, and only the second involving a crystal.

Quantum mechanical theory of dynamic nuclear polarization in solid dielectrics

Microwave driven dynamic nuclear polarization (DNP) is a process in which the large polarization present in an electron spin reservoir is transferred to nuclei, thereby enhancing NMR signal intensities. In solid dielectrics there are three mechanisms that mediate this transfer--the solid effect (SE), the cross effect (CE), and thermal mixing (TM). Historically these mechanisms have been discussed theoretically using thermodynamic parameters and average spin interactions. However, the SE and the CE can also be modeled quantum mechanically with a system consisting of a small number of spins and the results provide a foundation for the calculations involving TM. In the case of the SE, a single electron-nuclear spin pair is sufficient to explain the polarization mechanism, while the CE requires participation of two electrons and a nuclear spin, and can be used to understand the improved DNP enhancements observed using biradical polarizing agents. Calculations establish the relations among the electron paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR) frequencies and the microwave irradiation frequency that must be satisfied for polarization transfer via the SE or the CE. In particular, if δ, Δ < ω(0I), where δ and Δ are the homogeneous linewidth and inhomogeneous breadth of the EPR spectrum, respectively, we verify that the SE occurs when ω(M) = ω(0S) ± ω(0I), where ω(M), ω(0S) and ω(0I) are, respectively, the microwave, and the EPR and NMR frequencies. Alternatively, when Δ > ω(0I) > δ, the CE dominates the polarization transfer. This two-electron process is optimized when ω(0S(1))-ω(0S(2)) = ω(0I) and ω(M)~ω(0S(1)) or ω(0S(2)), where ω(0S(1)) and ω(0S(2)) are the EPR Larmor frequencies of the two electrons. Using these matching conditions, we calculate the evolution of the density operator from electron Zeeman order to nuclear Zeeman order for both the SE and the CE. The results provide insights into the influence of the microwave irradiation field, the external magnetic field, and the electron-electron and electron-nuclear interactions on DNP enhancements.

Accurate determination of the spin Hamiltonian parameters for Mn 2+ ions in cubic ZnS nanocrystals by multifrequency EPR spectra analysis

Accurate determination of the spin Hamiltonian (SH) parameters, describing the electron paramagnetic resonance (EPR) spectra of paramagnetic impurity ions in wide band gap semiconductor nanocrystals, is essential for determining their localization and quantum properties. Here we present a procedure, based on publicly available software, for determining with higher accuracy the SH parameters of isolated Mn 2+ impurity ions in small cubic ZnS nanocrystals. The procedure, which can be applied to other cubic II–VI semiconductor nanocrystals as well, is based on the analysis of both low and high frequency EPR spectra with line shape simulation and fitting computing programs, which include the hyperfine forbidden transitions and line broadening effects. The difficulties, limitations and errors which can affect the accuracy in determining some of the SH parameters are also discussed.

A high-frequency EPR characterization of the S = 2 linear tri-atomic chain in Cr 3(dpa) 4Cl 2·CH 2Cl 2

We report the high frequency electron paramagnetic resonance (HF-EPR) study of Cr 3(dpa) 4Cl 2, a linear tri-atomic (Cr II ) 3 chain, that was reported to be EPR silent at the X-band (9.5 GHz). Higher frequencies yield well resolved spectra for this S = 2 system even at room temperature. At 30 K, our variable frequency (34–400 GHz) EPR spectra yield a large axial zero-field splitting ( D) of −1.643(1) cm −1 as well as a small rhombic ZFS parameter E = 0.0339(4) cm −1; with g x = 1.9978(4), g y = 1.9972(4), and g z = 1.9808(4). The magnetic susceptibility measurements fully support the earlier magnetic susceptibility studies and the current EPR results. The observation of the EPR spectrum of only the S = 2 state at room temperature suggests that the ground state is well isolated from the excited states.

A high field and frequency electron paramagnetic resonance study of the S = 2 chromium(II) complex trans-[Cr(NCCH 3) 4(FBF 3) 2] and investigation of its reaction with dioxygen: Crystal structure of [(CH 3CN) 5CrOCr(NCCH 3) 5](BF 4) 4·2CH 3CN

From high field and frequency electron paramagnetic resonance (EPR) powder spectra of the high spin chromium(II) complex trans-[Cr(NCCH 3) 4(FBF 3) 2] ( 1) recorded at T = 5–40 K the EPR parameters were found to be D = −2.19 cm −1, E ≈ 0 cm −1, and g ‖ = g ⊥ = 1.9833. The reaction between a MeCN solution of 1 and dioxygen gave dark green crystals of [(CH 3CN) 5CrOCr(NCCH 3) 5](BF 4) 4·2CH 3CN ( 2). From the X-ray crystal structure of 2 at T = 122 K a Cr–O–Cr angle of 180° and a Cr–O distance of 1.7556(5) Å was found. This is the shortest among the known Cr–O distances in dinuclear complexes containing a CrOCr 4+ core, and this can partly explain the strong antiferromagnetic coupling between the two chromium(III) centers in 2.

Theoretical Calculation of the Magnetic Resonance Frequency of the Electron Spin Embedded Inside a Silicon Host for Solid-State Quantum Computing

The electron-spin magnetic resonance frequency of an electron-spin qubit structure that is proposed for the realization of a quantum computer is rigorously determined by a numerical method. The potential distribution inside the silicon qubit structure is accurately calculated by an electromagnetic simulation method, and the perturbation theory to the second order is formulated to obtain the magnetic resonance frequency of a phosphorus donor electron spin. Our results showed that, for the same qubit structure (Si:P), as originally proposed by Kane for a nuclear-spin qubit quantum computer, a smaller static magnetic field <i xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">B</i> is in favor of producing a wider tunable bandwidth for the magnetic resonance frequency of the electron spin. Our results also reveal that the use of SiGe as an alternative insulation material to the A-gate structure can improve the control efficiency of the A-gate voltage.

Anomalous Magnetism and Quantum Critical Phenomena in VOx Multi-Walled Nanotubes

High frequency (60 GHz) electron spin resonance (ESR) and magnetic susceptibility were studied for VO x multi-walled nanotubes (VOx-NTs) in the range of 4.2–300 K. It is found that apart from technological impurities, the magnetism of VOx-NTs is controlled by (i) antiferromagnetic V4+ noninteracting dimmers and (ii) V4+ quasi-free spins, which at T < 50 K form a disorder driven quantum critical state. From concentration estimates, we argue the V4+ dimers are an essential element of the VO x -NTs structure.

Detection and Identification of Nitrogen Centers in Nanodiamond: EPR Studies

Electron paramagnetic resonance (EPR) and electron spin echo (ESE) at X-band and at high-frequency W-band (95 GHz) have been used to study natural diamond nanocrystals, detonation nanodiamond (ND) with a size of ∼ 4.5 nm and detonation ND after high-temperature, high-pressure sintering with a size of ∼ 8.5 nm. Isolated nitrogen centers N0 and nitrogen pairs N2 + have been detected and identified, and their structure has been unambiguously determined by means of the high frequency EPR and ESE in natural diamond nanocrystals. In detonation ND and detonation ND after sintering, isolated nitrogen centers N0 have been discovered in nanodiamond core. In addition EPR signals of multivacancy centers with spin 3/2 seem to be observed in nanodiamond core of detonation ND.

Torque detected broad band electron spin resonance

We present a novel technique to measure high frequency electron spin resonance spectra in a broad frequency range (30-1440 GHz) with high sensitivity. We use a quasioptical setup with tunable frequency sources to induce magnetic resonance transitions. These transitions are detected by measuring the change in the magnetic torque signal by means of cantilever torque magnetometry. The setup allows tuning of the frequency, magnetic field, polarization, and the angle between the sample and the external magnetic field. We demonstrate the capabilities of this technique by showing preliminary results obtained on a single crystal of an Fe(4) molecular nanomagnet.

Nitrogen Centers in Nanodiamonds: EPR Studies

Electron paramagnetic resonance (EPR) and electron spin echo (ESE) at X-band (9.4 GHz) and W-band (94 GHz) have been used to study defects in natural diamond nanocrystals, detonation nanodiamond (ND) with a size of  4.5 nm and detonation ND after high-pressure high-temperature (HTHP) sintering with a size of  8.5 nm. Based on identification of atomic nitrogen centers N0 and nitrogen pairs N2+ detected by means of the high frequency EPR and ESE in natural diamond nanocrystals, atomic nitrogen centers N0 have been discovered in nanodiamond core in detonation ND and detonation ND after sintering. In addition EPR signal of multi-vacancy centers with spin 3/2 seems to be observed in diamond core of detonation ND.

In vivo temporal EPR study using a region-selected intensity determination method to estimate cerebral reducing ability in rats treated with olanzapine

Region-selected intensity determination (RSID) is a method for obtaining the temporal changes in electron paramagnetic resonance (EPR) signal intensity from a target region, without the use of complicated procedures employed in the conventional imaging methods. An in vivo 700-MHz radio frequency EPR spectrometer equipped with a bridged loop-gap resonator was used with the RSID method to estimate intracerebral reducing ability in the rat following acute administration of olanzapine (OZP) or haloperidol (HPD). To this end, temporal changes in EPR signal intensity of target regions (the striatum and the prefrontal cortex) of rats which had received a blood-brain-barrier-permeable nitroxide radical (3-hydroxymethyl-2,2,5,5-tetramethylpyrrolidine-1-oxyl) via an intravenous route were observed. The half-lives of EPR signal intensity in both regions of OZP- or HPD-treated rats were significantly longer than in control animals. This indicated that reducing abilities of the striatum and cerebral cortex decreased in the rats to which either OZP or HPD had been acutely administered.

Multifrequency EPR studies of manganese catalases provide a complete description of proteinaceous nitrogen coordination.

Pulse electron paramagnetic resonance (EPR) spectroscopy is employed at two very different excitation frequencies, 9.77 and 30.67 GHz, in the study of the nitrogen coordination environment of the Mn(III)Mn(IV) state of the dimanganese-containing catalases from Lactobacillus plantarum and Thermus thermophilus. Consistent with previous studies, the lower-frequency results reveal one unique histidine nitrogen-Mn cluster interaction. For the first time, a second, more strongly hyperfine-coupled (14)N atom is unambiguously observed through the use of higher frequency/higher field EPR spectroscopy. The low excitation frequency spectral features are rationalized as arising from the interaction of a histidine nitrogen that is bound to the Mn(IV) ion, and the higher excitation frequency features are attributed to the histidine nitrogen bound to the Mn(III) ion. These results allow for the computation of intrinsic hyperfine coupling constants, which range from 2.2 to 2.9 MHz, for sp(2)-hybridized nitrogens coordinating equatorially to high-valence Mn ions. The relevance of these findings is discussed in the context of recent results from analogous higher frequency EPR studies of the Mn cluster in photosystem II and other exchange-coupled, transition metal-containing systems.